Q.(a) Explain hydrate (solvate) isomerism and linkage isomerism with suitable examples.
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Start your 14-day free trial to unlock the full solution →(a) Hydrate isomerism arises from water being either a coordinated ligand or lattice water; linkage isomerism arises from an ambidentate ligand binding through either of its two donor atoms. (b) -labelled water traces the origin of photosynthetic oxygen (from water) and the site of bond cleavage in ester hydrolysis (the acyl–oxygen bond).
(a) Hydrate (solvate) isomerism
This type of isomerism arises among hydrated coordination compounds when water molecules can be distributed differently between (i) the coordination sphere, where they act as ligands directly bonded to the metal, and (ii) the crystal lattice, where they exist as "water of crystallisation" and are not bonded to the metal. Because the total formula (e.g. ) is the same in every isomer, but the number of ligands actually coordinated differs, the isomers differ in colour, conductivity (number of free ions), and reactivity.
Classic example — has three known hydrate isomers:
- — violet; all 3 ions are free (ionisable), giving the highest conductivity.
- — grey-green; 2 free ions, 1 lattice water; intermediate conductivity.
- — dark green; only 1 free ion, 2 lattice waters; lowest conductivity.
These can be distinguished experimentally by titrating a solution against : the number of ions precipitated as immediately corresponds to the number of free (ionic) chloride ions, not the total chlorine content.
Linkage isomerism
This arises when the complex contains an ambidentate ligand — a ligand possessing two different atoms, either of which can act as the donor atom to the metal. Depending on which atom binds the metal, different (linkage) isomers result.
Common ambidentate ligands: (can bind through N as "nitro" or through O as "nitrito"), (can bind through S as "thiocyanato" or through N as "isothiocyanato").
Example:
- — pentaamminenitrito-N-cobalt(III) chloride (nitro form, Co–N bond), yellow-brown, stable.
- — pentaamminenitrito-O-cobalt(III) chloride (nitrito form, Co–O bond), red, less stable, isomerises to the nitro form on standing/heating.
(b) Radioactive (isotopic) tracer studies
Mechanism of photosynthesis: The overall photosynthesis equation is , but it was originally unclear whether the evolved oxygen came from or from . In the classic tracer experiment (Ruben and Kamen), plants were supplied with water enriched in the heavy isotope (i.e. ) together with ordinary (unlabelled) . The gas evolved by the plant was found to be enriched in , matching the label in the water, not in the . This proved that the oxygen liberated in photosynthesis originates entirely from the photolysis (splitting) of water, and not from carbon dioxide:
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